EP0228095B1 - Verfahren zur Herstellung von Silanen und Siloxanen - Google Patents

Verfahren zur Herstellung von Silanen und Siloxanen Download PDF

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Publication number
EP0228095B1
EP0228095B1 EP86118123A EP86118123A EP0228095B1 EP 0228095 B1 EP0228095 B1 EP 0228095B1 EP 86118123 A EP86118123 A EP 86118123A EP 86118123 A EP86118123 A EP 86118123A EP 0228095 B1 EP0228095 B1 EP 0228095B1
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Prior art keywords
reaction
catalyst
olefin
dimethylamino
silane
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French (fr)
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EP0228095A3 (en
EP0228095A2 (de
Inventor
Jennifer Maryann Quirk
Bernard Kanner
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0801—General processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages

Definitions

  • the present invention relates to a novel process for the preparation of compounds having one of the following formulas (A) or (B): wherein R, R1, R2, R3, R4, R5, and R6 are individually alkyl or aryl groups containing from 1 to 8 carbon atoms, R8 and R9 are individually hydrogen, alkyl, alkeny, aryl, alkoxy, aryloxy, polyether, alkylsilyl, alkoxysilyl or aminosilyl groups having from 1 to 50 carbon atoms, a has a value of 0 to 1, b has a value of 0 to 1, x has a value of 1,2 or 3, y has a value from 0 to 500, z has a value from 0 to 500 and the sum of y and z equals from 0 to 500 with the proviso, that if z has a value of 0, the sum of a and b mustequal at least one.
  • the process provides the dehydrocondensation of a silicon-containing compound with a olefin in the presence of a rhodium or ruthenium catalyst in a one-step process.
  • hydrosilation reaction between a silane and an olefin is generally depicted as follows:
  • osmium compounds such as chloroosmic acid
  • osmium compounds are very expensive and thus other routes have been explored, such as in GB - A - 1,365,431 where nickel complexes are disclosed as catalyzing the reaction of ⁇ SiH compounds with olefins to provide organosilicon compounds having olefinic unsaturation.
  • Ru3(CO)12 was reported to catalyze a dehydrocondensation reaction between simple silanes and olefins in Angew. Chem. Int. Ed. Engl. 19 (1980) 928.
  • Rhodium catalysts were unexpectedly found to yield E-hex-1-en-1-yl(triethyl)silane and E-hex-2-en-1-yl(triethyl)silane when triethylsilane and hex-1-ene were reacted together in Journal of Molecular Catalysis, 26 (1984) 89-104.
  • the objective of the present invention is to provide a one-step process which will synthesize olefinic silanes and/or siloxanes of the given formulas (A) and (B) by a process which has yields that are high enough to be commercially attractive and which minimizes by-products and in particular hydrogenation and hydrosilation products.
  • Hindered alkoxysilanes such as tri- tert .butoxysilane and tri- iso propoxysilane have also unexpectedly been shown to undergo dehydrocondensation whereas less hindered alkoxysilanes such as trimethoxysilane and triethoxysilane favor hydrosilation under identical conditions, though some dehydrocondensation products have been observed as reported above.
  • Simple siloxanes such as bis(trimethylsiloxy)methylsilane and heptamethylcyclotetrasiloxane and Si-H fluids also undergo dehydrocondensation. This is unexpected in that siloxanes are well known to undergo rapid hydrosilation.
  • R, R1 and R2 are either methyl or phenyl and x has a value of 3.
  • the secondary aminosilanes may be purchased commercially or prepared from any of a variety of known techniques, such as described in Eaborn, Organosilicon Compounds , Academic Press Inc., New York, 1690, p. 339.
  • Suitable secondary aminosilanes include, dimethylaminodimethylsilane, bis(dimethylamino)methylsilane, tris(dimethylamino)silane, dimethylaminomethylethylsilane, diethylaminoethylpropylsilane, diethylaminomethylethylsilane, diphenylaminomethylethylsilane, diphenylaminomethylphenylsilane, dibenzylaminoethylphenylsilane, diphenylaminodimethylsilane, bis(diethylamino)ethylsilane, bis(dimethylamino)ethylsilane, bis(dibenzylamino)methylsilane, tris(diethylamino)silane, tris(piperidino)silane, and tris(dicyclohexylamino)silane. Most preferably the secondary amino
  • Siloxanes preferably useful in the dehydrogenative silylation are those represented by the general formula (D) wherein the alkyl group is methyl and the aryl group is phenyl. These siloxanes may be purchased commercially or prepared from any of a variety of known techniques, such as described in Eaborn, Organosilicon Compounds , Academic Press Inc., New York, 1960, p. 228.
  • Suitable siloxanes include bis(trimethylsilyloxy)methylsilane, 1,1,3,3-tetramethyldisiloxane, and heptamethylcyclotetrasiloxane. Most other siloxanes are generally mixtures of a variety of siloxanes. Preferably the siloxane is such that R3, R4, R5 and R6 are all methyl groups.
  • R8 and R9 are preferably hydrogen or one of the above groups having from 1 to 10 carbon atoms.
  • the olefins can be purchased commercially.
  • Olefins which are suitable for use in the practice of this invention, are, known compounds and include, the following: ethylene, propylene, iso butylene, styrene, iso prene, butadiene, allylmethoxytriglycol, and vinylsilanes, including vinyltriethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri iso propoxysilane, vinyltri tert butoxysilane, vinyltris(dimethylamino)silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, and vinyldimethylethoxysilane.
  • olefins which are suitable include functional olefins such as allylamine, acrylate and methacrylate esters, and unsaturated ketones.
  • the reaction takes place in the presence of a rhodium or ruthenium catalyst.
  • the rhodium or ruthenium catalyst may be used neat; on a support such as carbon black or alumina; or in a solvent as a soluble compound of rhodium or ruthenium, i.e., chlorodicarbonylrhodium(I) dimer, dodecarbonyltetrarhodium(0), acetylacetonatodicarbonylrhodium(I).
  • chloro(1,5-cyclooctadiene)rhodium(I) dimer dodecacarbonyltriruthenium(0) tris(acetylacetonato)ruthenium(III), and complexes of rhodium and ruthenium with phosphines, such as tristriphenylphosphinerhodium(I) chloride, tristriphenylphosphinerhodium(I) carbonylhydride and dichlorotris(triphenylphosphine)ruthenium(II).
  • the catalysts are available commercially.
  • the concentration of the catalyst is normally between 0.000010-0.05 mole % with respect to the silicon composition, it is preferred however to use no more catalyst than required to obtain the necessary reaction due to the significant costs associated with catalysts of this type. However, impurities common in many olefins may necessitate higher concentrations.
  • the dehydrocondensation should be run at temperatures greater than 40°C with the optimum temperature being between 100-200°C. Although the upper temperature limit is not critical, the reaction should be run below the decomposition point of the starting materials or products.
  • the reaction can be run at atmospheric pressure. Increasing or decreasing the pressure would not be expected to generate anything other than one skilled in the art would expect, i.e. alter reaction rates.
  • the reaction may be carried out with or without a solvent. When a solvent is desirable for reasons such as solubility or temperature control, a solvent may be used. Suitable solvents are hydrocarbons such as octane, toluene, xylene or tri iso propylbenzene.
  • the order of the addition of the reactants is not important, although normally, the rhodium or ruthenium catalyst is added to the silicon composition and olefin and then heat is applied. A ratio of 1:2 to 1:5 of the silicon composition to the olefin is preferred. This is done to minimize the reaction of hydrogen generated in the reaction with the olefinic silane or siloxane.
  • silanes and siloxanes which can be prepared according to the process of the invention find utility as coupling agents in a variety of applications including mineral filled composites and fiber glass applications; crosslinking agents for polymers; compounding agents for dental impressions; and encapsulated gels to name but a few.
  • the reaction was run as described in Example 1 except that a 1 : 1 mole ratio of tris(dimethylamino)silane and ethylene was used.
  • the product mixture after the reaction was complete was shown to contain 20.3% tris(dimethylamino)silane, 23,6 % vinyltris(dimethylamino)silane and 51,7 % ethyltris(dimethylamino)silane.
  • Example 2 The reaction was run as described in Example 1 except that triisopropoxysilane was used as as the starting silicon composition. After the reaction was complete the product mixture was shown to contain approximately 85% vinyltriisopropoxysilane, 7 % ethyltriisopropoxysilane and 3 % tetraisopropoxysilane.
  • the reaction was run as described in Example 1 except that tri-tert.butoxysilane was used as the starting silicon composition.
  • the product mixture was shown to contain 96% vinyltri-tert.butoxysilane and 2 % ethyltri-tert.butoxysilane.
  • the reaction was run as described in Example 1 except that triethoxysilane was used as the starting silicon composition.
  • the product mixture was shown to contain 62% vinyltriethoxysilane, 28 % ethyltriethoxysilane and 6 % tetraethoxysilane.
  • the reaction was run as described in Example 1 except that trimethoxysilane was used as the starting silicon composition.
  • the product mixture was shown to contain 12% vinyltrimethoxysilane, 78 % ethyltrimethoxysilane and 4 % tetramethoxysilane.
  • the reaction was run as described in Example 1 except that bis(trimethylsiloxy)methylsilane was used as the starting silicon composition.
  • the product mixture was shown to contain 72% vinylbis(trimethylsiloxy)methylsilane and 25 % ethylbis(trimethylsiloxy)methylsilane.
  • the reaction was run as described in Example 1 except that heptamethylcyclotetrasiloxane was used as the starting silicon composition.
  • the product mixture was shown to contain 62% vinylheptamethylcyclotetrasiloxane and 36 % ethylheptamethylcyclotetrasiloxane.
  • the reaction was run as described in Example 1 except 1000 ppm Ru3CO12 was used as the catalyst.
  • the product mixture was shown to contain 57.5% Vinyltris(dimethylamino)silane and 40.2% ethyltris(dimethylamino)silane.
  • the reaction was run as described in Example 1 except that 10 ppm Rh/C was used as the catalyst.
  • the product mixture contained 80.1% vinyltris(dimethylamino)silane and 9.9% ethyltris(dimethylamino)silane.
  • a one liter, 3-necked flask was equipped with a stirring bar, thermometer, 500 ml addition funnel and reflux condenser topped with a nitrogen inlet tube.
  • the flask was charged with 200.0 g (1.21 mol) tris(dimethylamino)silane, 2.27 g phenothiazine and 200 ppm Rh2Cl2CO4 (80 mg) as a catalyst.
  • the solution was heated to 120°C at which time 228 g (2.24 mol) styrene was added dropwise over a period of 2 hours. There was an initial exotherm reaction to 150°C and the temperature was then maintained between 120-150°C. After the addition was complete the reaction mixture was cooled to room temperature.
  • GC and GC/MS confirmed that a single product, 1-tris(dimethylamino)silyl-2-phenylethylene was formed in greater than 90 % yield.
  • Example 17 The reaction was run as described in Example 17 except that triisopropoxysilane was used as the starting silicon composition. Two products were formed in a 3 to 1 ratio. The major one was 1-triisopropoxysilyl-2-phenylethylene and the minor one 1-triisopropoxysilyl-2-phenylethane.
  • Example 17 The reaction was run as described in Example 17 except that triethoxysilane was used as the starting silicon composition. Two products were formed in a 2 to 1 ratio. The major one was 1-triethoxysilyl-2-phenylethane and the minor one was 1-triethoxysilyl-2-phenylethylene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Silicon Polymers (AREA)

Claims (7)

  1. Verfahren zur Herstellung von Verbindungen die einer der beiden folgenden Formeln (A) oder (B) entsprechen:
    Figure imgb0018
     in denen
       R, R¹, R², R³, R⁴, R⁵ und R⁶ jeweils für Alkyl- oder Arylgruppen mit 1 bis 8 Kohlenstoffatomen stehen, R⁸ und R⁹ jeweils Wasserstoff, Alkyl-, Alkenyl-, Aryl-, Alkoxy-, Aryloxy-, Polyether-, Alkylsilyl-, Alkoxysilyl- oder Aminosilylgruppen mit 1 bis 50 Kohlenstoffatomen bedeuten,
    a einen Wert von 0 bis 1 hat,
    b einen Wert von 0 bis 1 hat,
    x einen Wert von 1, 2 oder 3 hat,
    y einen Wert von 0 bis 500 hat,
    z einen Wert von 0 bis 500 hat
    und die Summe von y und z gleich 0 bis 500 ist mit der Maßgabe, daß wenn z einen Wert von 0 hat, die Summe von a und b mindestens 1 sein muß,

    dadurch gekennzeichnet, daß entweder ein sekundäres Aminosilan der allgemeinen Formel (C):



            (C)   H-Si(NRR¹)x(R²)3-x



    in der R, R¹ , R² und x die angegebene Bedeutung haben, oder ein Siloxan der allgemeinen Formel (D):
    Figure imgb0019
     in der R³, R⁴, R⁵, R⁶, a, b und y die angegebene Bedeutung haben, mit einem Olefin der allgemeinen Formel (E):
    Figure imgb0020
     in der R⁸ und R⁹ die angegebene Bedeutung haben, in Gegenwart eines Rhodium- oder Rutheniumkatalysators, umgesetzt wird.
  2. Verfahren nach Anspruch 1, worin der Katalysator unter Ru₃(CO)₁₂, [Rhcl(CO)₂]₂, Ru₄(CO)₁₂, RuCl₂(CO)₂(PPh₃)₂, Ru(C₅H₇O₂)₃, RuCl(PPh₃)₃, Rh/C und RhCl(PPh₃)₃ ausgewählt wird.
  3. Verfahren nach Anspruch 1, worin der Katalysator in einer Konzentration von 0,000010 bis 0,05 mol-%, bezogen auf die Siliciumverbindung, vorhanden ist.
  4. Verfahren nach Anspruch 1, worin ein Lösungsmittel, vorzugsweise unter Octan, Toluol, Xylol, Chlorbenzol und 1,3,5-Triisopropylbenzol ausgewählt, verwendet wird.
  5. Verfahren nach Anspruch 1, worin das Verhältnis von Siliciumverbindung zu Olefin 1:2 bis 1:5 beträgt.
  6. Verfahren nach Anspruch 1, worin das Olefin unter: Vinyltriethoxysilan, Vinyltris(dimethylamino)silan und Vinyltriisopropoxysilan ausgewählt wird.
  7. Verfahren nach Anspruch 1, worin das Olefin unter Butadien und Isopren ausgewählt wird.
EP86118123A 1985-12-31 1986-12-30 Verfahren zur Herstellung von Silanen und Siloxanen Expired - Lifetime EP0228095B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/815,003 US4668812A (en) 1985-12-31 1985-12-31 Process for the preparation of olefinic silanes and siloxanes
US815003 1997-03-14

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EP0228095A2 EP0228095A2 (de) 1987-07-08
EP0228095A3 EP0228095A3 (en) 1988-08-03
EP0228095B1 true EP0228095B1 (de) 1992-01-22

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US (1) US4668812A (de)
EP (1) EP0228095B1 (de)
JP (1) JPS62164688A (de)
AU (1) AU598780B2 (de)
BR (1) BR8606482A (de)
CA (1) CA1290762C (de)
DE (1) DE3683617D1 (de)

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US4946818A (en) * 1988-04-05 1990-08-07 General Electric Company Rhodium colloid, method of making, and use
JP2507898B2 (ja) * 1990-06-13 1996-06-19 工業技術院長 アルケニルシラン化合物およびその製造方法
US5041595A (en) * 1990-09-26 1991-08-20 Union Carbide Chemicals And Plastics Technology Corporation Method for manufacturing vinylalkoxysilanes
JPH0517486A (ja) * 1991-07-04 1993-01-26 Shin Etsu Chem Co Ltd 有機ケイ素化合物及びその製造方法
FR2709757B1 (fr) * 1993-09-07 1995-11-17 Rhone Poulenc Chimie Procédé de préparation de polyorganosiloxanes à fonctions insaturées par déshydrogénocondensation en présence de complexes de métaux du groupe IV.
US6492480B1 (en) * 1999-10-28 2002-12-10 Japan Science And Technology Corporation Method of polymerizing a silalkylenesiloxane
PL2076521T3 (pl) * 2006-08-16 2013-06-28 Univ Adama Mickiewicza Sposób otrzymywania sililopodstawionych 1,2 alkinów
US20080312356A1 (en) * 2007-06-13 2008-12-18 Applied Mcrostructures, Inc. Vapor-deposited biocompatible coatings which adhere to various plastics and metal
JP5170834B2 (ja) * 2008-04-22 2013-03-27 信越化学工業株式会社 脱アルコール型室温硬化性シリコーンゴム組成物の保存安定性付与剤
US20100144897A1 (en) * 2008-12-08 2010-06-10 O'lenick Jr Anthony J Methicone replacements for cyclomethicone
JP6125222B2 (ja) * 2012-08-16 2017-05-10 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド コバルト触媒を用いる脱水素シリル化および架橋
WO2015159569A1 (ja) * 2014-04-15 2015-10-22 信越化学工業株式会社 アルコキシシリル－ビニレン基含有ケイ素化合物
JP6424840B2 (ja) * 2016-01-12 2018-11-21 信越化学工業株式会社 １，２−ビスシリルエチレン化合物の製造方法
JP6432537B2 (ja) * 2016-02-09 2018-12-05 信越化学工業株式会社 ビスシリル化合物およびその製造方法

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DE1125619B (de) * 1960-07-08
US3595733A (en) * 1969-07-09 1971-07-27 Dow Chemical Co Method of preparing alpha-unsaturated organosilicon compounds
BE755943A (fr) * 1969-09-10 1971-03-09 Rhone Poulenc Sa Procede de preparation de composes organosiliciques insatures
GB1365431A (en) * 1973-01-31 1974-09-04 Dow Corning Ltd Process for preparing organosilicon products
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JPS57140788A (en) * 1981-02-25 1982-08-31 Sagami Chem Res Center Preparation of vinylsilane having perfluoro group

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EP0228095A3 (en) 1988-08-03
JPH0353317B2 (de) 1991-08-14
US4668812A (en) 1987-05-26
AU6704786A (en) 1987-07-02
EP0228095A2 (de) 1987-07-08
DE3683617D1 (de) 1992-03-05
JPS62164688A (ja) 1987-07-21
AU598780B2 (en) 1990-07-05
BR8606482A (pt) 1987-10-20
CA1290762C (en) 1991-10-15

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